The one-pot Diels-Alder cycloaddition (DAC)/dehydration (D) tandem reaction between 2,5-dimethylfuran and ethylene is a potent pathway toward biomass-derived p-xylene. In this work, we present a cheap and active low-silica potassium-exchanged faujasite (KY, Si/Al = 2.6) catalyst. Catalyst optimization was guided by a computational study of the DAC/D reaction mechanism over different alkali-exchanged faujasites using periodic density functional theory calculations complemented by microkinetic modeling. Two types of faujasite models were compared, i.e., a high-silica alkali-exchanged faujasite model representing isolated active cation sites and a low-silica alkali-exchanged faujasite in which the reaction involves several cations in the proximity. The mechanistic study points to a significant synergetic cooperative effect of the ensemble of cations in the faujasite supercage on the DAC/D reaction. Alignment of the reactants by their interactions with the cationic sites and stabilization of reaction intermediates contribute to the high catalytic performance. Experiments confirmed the prediction that KY is the most active catalyst among low-silica alkali-exchanged faujasites. This work is an example of how the catalytic reactivity of zeolites depends on multiple interactions between the zeolite and reagents.@en

The concept of liquid metal membranes for hydrogen separation, based on gallium or indium, was recently introduced as an alternative to conventional palladium-based membranes. The potential of this class of gas separation materials was mainly attributed to the promise of higher hydrogen diffusivity. The postulated improvements are only beneficial to the flux if diffusion through the membrane is the rate-determining step in the permeation sequence. Whilst this is a valid assumption for hydrogen transport through palladium-based membranes, the relatively low adsorption energy of hydrogen on both liquid metals suggests that other phenomena may be relevant. In the current study, a microkinetic modeling approach is used to enable simulations based on a five-step permeation mechanism. The calculation results show that for the liquid metal membranes, the flux is limited by the dissociative adsorption over a large temperature range, and that the membrane flux is expected to be orders of magnitude lower compared to the membrane flux through pure palladium membranes. Even when accounting for the lower cost of the liquid metals compared to palladium, the latter still outperforms both gallium and indium in all realistic scenarios, in part due to the practical difficulties associated with making liquid metal thin films.@en